A facile one-step hydrothermal method was developed to synthesize novel hierarchical rose-like Bi2O2CO3 microstructures. The physico-chemical properties of the as-synthesized catalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, N2 adsorption–desorption and UV-visible diffuse reflectance spectroscopy. A possible formation mechanism of hierarchical Bi2O2CO3 microspheres was proposed. The photocatalytic activity of the as-prepared samples was evaluated toward degradation of rhodamine B, and mixed aqueous solutions containing methylene blue and methyl orange under visible-light. Compared to Bi2O2CO3 and Bi2WO6 nanosheets, hierarchical rose-like Bi2O2CO3 microspheres show enhanced photocatalytic activity. The observed photocatalytic performance was attributed to the synergetic effects of particle morphology, average crystallite size, specific surface area, pore structure, and exposed two-dimensional (2D) nanosheets with dominant {001} facets of 3D hierarchical rose-like Bi2O2CO3 microspheres.